Cosmetic compositions based on partly neutralized organic silicon compounds

ABSTRACT

The invention concerns a composition comprising in a cosmetically acceptable aqueous medium, at least 0.02 weight percent relative to the composition total weight, one or several water soluble organosilicon compounds, having one, two or three silicon atoms, at least a basic chemical function and at least two hydroxyl groups or groups capable of being hydrolyzed per molecule, said organosilicon compounds being partly neutralized with at least a neutralizing agent. The invention is applicable to hair care compositions.

This application is a 371 of PCT/FR99/02289 filed on Oct. 27, 1999.

The present invention relates generally to aqueous cosmeticcompositions, in particular for treating the hair, comprisingunpolymerized or relatively unpolymerized, water-soluble organosiliconcompounds.

It is common practice to use organic compounds such as polymers toprepare cosmetic compositions for treating the hair. For example,polymers are used that give, on drying, solid materials for fixing thehairstyle in a shape. Such materials are also used to give shape-holdingeffects. Polymer compounds, such as polysiloxanes, are also used to givehaircare effects, particularly to damaged hair or hair that is difficultto disentangle. Cosmetic compositions containing these polymers areapplied to the hair and left to dry or rinsed out before proceeding todry.

The use of polymer compounds presents many drawbacks.

The first drawback lies in the fact that, when the polymers are used incompositions above a certain concentration, the compositions obtainedare difficult to apply due to the increase in the viscosity of thecompositions. This difficulty in applying the compositions leads to thehair being overloaded in certain areas and thus to cosmetic defects andalso involves certain parts of the hair receiving less of thecompositions, which, in the end, induces a reduced effect on theseareas.

The second drawback lies in the fact that these compositions areoccasionally difficult to use. Specifically, polymer compounds of lowwater solubility require the use of an organic solvent or a mixture oforganic solvents. The use of an organic solvent entails severalproblems, for instance environmental problems and problems affecting thecosmetic quality of the hair.

To overcome these drawbacks, attention has thus turned toward the use ofpolymer compounds that have been made partially water-soluble. Thus,certain polymer compounds may be used in water without adding anyco-solvent. In this case, the limitation lies in the fact that thesepolymer compounds are partially, or even totally, removed by rinsing thehair. Consequently, in this case, the effect due to the polymercompounds is very limited after rinsing. Ultimately, this limits theeffect of rinse-out treatments (shampooing, conditioning), but alsoreduces the advantage of such compositions used in leave-in mode(hairsetting lotions, mousses, lacquers, etc.) since the user loses theeffect acquired by the treatment when the user washes the hair.

Efforts have thus been devoted toward finding compounds for formulatingcosmetic compositions that can be used in water and that retain theireffect when the hair is rinsed.

Thus, U.S. Pat. No. 4,344,763 (Gillette) describes cosmetic compositionscomprising an organosiloxane monomer such as an aminoalkylalkoxysilaneand an organic titanate dissolved in an alcohol.

More specifically, the patent describes a process for shaping the hairwhich consists in moistening the hair with water and then in applying asolution containing, in isopropanol, from 0.5% to 15% by weight of anaminoalkylalkoxysilane and from 0.005% to 1.5% by weight of an organictitanate, and then in placing the hair in the desired shape.

According to this process, it is particularly recommended to keep theisopropanol solution protected from any moisture.

A process has also been disclosed, in EP 113 992, for simultaneouslyfixing and conditioning the hair using a composition that is stable inthe absence of moisture, containing (A) a siloxane oligomer containingat least one nitrogen-hydrogen bond, and (B) an anhydrous, readilyhydrolyzable additive chosen from titanates, zirconates, vanadates,germanates, and mixtures thereof.

The solvent for the composition is an aliphatic hydrocarbon or analiphatic halohydrocarbon, preferably 1,1,1-trichloroethane.

After applying the composition to the hair, the hair is placed in ahumid atmosphere so as to bring about the crosslinking of the siloxaneoligomer and of the readily hydrolyzable anhydrous additive.

There is thus a need for a stable cosmetic composition, in particularfor treating the hair, which is essentially aqueous and which makes itpossible to obtain a sufficient cosmetic effect, in particular for thehair, in rinse-out or leave-in mode.

One subject of the present invention is thus stable, aqueous cosmeticcompositions, in particular cosmetic compositions for hair treatment andhaircare, which overcome the drawbacks of the prior art.

More specifically, one subject of the present invention is stable,aqueous cosmetic compositions for hair treatment and haircare, whichgive the hair a long-lasting styling effect and a pleasant feel.

The inventors have found, surprisingly, that it is possible to formulatecosmetic compositions not requiring the use of an organic solvent andhaving an effective, rinse-fast cosmetic effect, without the risk ofproblems of the hair being charged in the event of overloading, by usingin these compositions unpolymerized or relatively unpolymerized,water-soluble organosilicon compounds comprising at least one basic andpartially neutralized chemical function.

It has been observed that when such compositions are applied, pronouncedcosmetic effects are obtained without any problems in the event ofoverloading, and the effects of which are very rinse-fast and wash-fast.

According to the invention, the cosmetic compositions, in particular fortreating the hair, comprise, in a cosmetically acceptable aqueousmedium, at least 0.02% by weight, relative to the total weight of thecomposition, of one or more unpolymerized or relatively unpolymerized,water-soluble organosilicon compounds chosen from organosilanescomprising one silicon atom and organosiloxanes comprising two or threesilicon atoms, the organosilicon compounds also comprising at least onebasic chemical function and at least two hydrolyzable or hydroxyl groupsper molecule, characterized in that the compositions comprise an amountof a neutralizing agent such that the unpolymerized or relativelyunpolymerized organosilicon compounds are neutralized to a proportion offrom 1/1000 to 99/100 and preferably from 0.2/100 to 70/100.

The organosilicon compounds according to the invention are capable offorming, in aqueous medium, a nonhybrid compound, afterself-condensation and evaporation of the support. The expression“nonhybrid compound” means a compound that is chemically homogeneous asregards silicon, that is to say that it contains no other additionalmetallic or organometallic species.

The unpolymerized or relatively unpolymerized organosilicon compoundsthat are useful in the compositions of the present invention are chosenfrom water-soluble organosilanes comprising one silicon atom andwater-soluble organosiloxanes comprising two or three silicon atoms,preferably two silicon atoms. They must also comprise at least one basicchemical function, and preferably only one basic chemical function. Thebasic chemical function may be any function that gives the siliconcompound a basic nature without harming its solubility in water and ispreferably an amine function such as a primary, secondary or tertiaryamine function. The basic chemical function of the silicon compoundsaccording to the invention may optionally comprise other functions suchas, for example, another amine function, an acid function or a halogenfunction.

The organosilicon compounds that are useful in the compositions of thepresent invention also comprise at least two hydrolyzable or hydroxylgroups per silicon atom. The hydrolyzable groups are preferably alkoxy,aryloxy or halogen groups. They may also optionally comprise otherchemical functions such as acid or amine functions.

The organosilanes that are preferred according to the inventioncorrespond to the formula:

in which:

-   -   R₄ represents a halogen or an OR′ or R′₁ group;    -   R₅ represents a halogen or an OR″ or R′₂ group;    -   R₆ represents a halogen or an OR″′ or R′₃ group;    -   and R₁, R₂, R₃, R′, R″, R″′, R′₁, R′₂ and R′₃ represent,        independently of each other, a saturated or unsaturated, linear        or branched hydrocarbon-based group optionally bearing        additional chemical groups such as acid or amine groups, R₁, R₂,        R′, R″ and R″′ also possibly denoting hydrogen, and    -   at least two of the groups R₄, R₅ and R₆ being other than the        groups R′₁, R′₂ and R′₃.

Preferably, R₁, R₂, R′, R″ and R″′, R′₁, R′₂ and R′₃ represent a C₁ toC₁₂ alkyl group, a C₆ to C₁₄ aryl group, a (C₁ to C₈)alkyl (C₆ toC₁₄)aryl group or a (C₆ to C₁₄)aryl(C₁ to C₈)alkyl group; and R₃ ispreferably a C₁ to C₁₂ alkyl group, a C₆ to C₁₄ aryl group, a (C₁ toC₈)alkyl (C₆ to C₁₄)aryl group or a (C₆ to C₁₄)aryl (C₁ to C₈)alkylgroup.

The organosiloxanes that are preferred in the compositions of thepresent invention may be represented by the formula:

in which:

-   -   R₁, R₂, R₃, R₅ and R₆ are defined as above;    -   R′₄ represents a halogen or an OR₁₁ group;    -   R₇ represents a halogen or an OR₁₀ or R″₁ group    -   R₉ represents a halogen or an OR₈, R″₂ or R₃NR₁R₂ group;    -   R″₁, R″₂, R₈, R₁₀ and R₁₁ represent a saturated or unsaturated,        linear or branched hydrocarbon-based group optionally bearing        additional chemical groups such as basic solubilizing groups;    -   R₁₁, R₁₀ and R₈ also possibly denoting hydrogen.

Preferably, R″₁, R″₂, R₈ or R₁₀ and R₁₁ represent a C₁ to C₁₂ alkylgroup, a C₆ to C₁₄ aryl group, a (C₁ to C₈)alkyl(C₆ to C₁₄)aryl groupand a (C₆ to C₁₄)aryl(C₁ to C₈)alkyl group.

At least one of the groups R₆, R₇ and R₉ denotes a halogen or a groupOR″′, OR₁₀ or OR₈.

Preferably, the halogen is chlorine.

One important aspect of the compositions of the invention is that theunpolymerized or relatively unpolymerized organosilicon compounds arepartially neutralized using a neutralizing agent or pH regulator, suchthat the neutralization reaches 1/1000 to 99/100 and better still from0.2/100 to 70/100. More preferably, the neutralization is from 0.2/100to 60/100.

The pH regulators may be any cosmetically acceptable acids or mixturesof acids. Among the acids that may be used, mention may be made ofhydrochloric acid, nitric acid and mono-, di- or tricarboxylic organicacids.

This partial neutralization of the unpolymerized or relativelyunpolymerized organosilicon compounds of the compositions of theinvention represents an important aspect for the production of thedesired properties for the compositions.

Another important aspect of the compositions according to the inventionis that the organosilicon compounds, the pH regulators and also theother constituents of the composition are chosen such that thiscomposition contains large amounts of the unpolymerized or relativelyunpolymerized organosilicon compounds, that is to say compoundscomprising one, two or three silicon atoms. Thus, it is necessary forthe composition to contain, relative to the total weight of thecomposition, at least 0.02% of unpolymerized or relatively unpolymerizedorganosilicon compounds and preferably at least 0.5% by weight, possiblyranging up to 50% by weight.

The content of unpolymerized or relatively unpolymerized organosiliconcompounds according to the invention is determined by the usual analysismethods such as silicon-29 and proton NMR spectroscopy, and bychromatography.

The compositions according to the invention are aqueous compositions.However, it is possible, for example for the use of adjuvants, to add acosolvent such as an alcohol or a ketone, for example ethanol oracetone.

In a known manner, all the compositions of the invention may containadjuvants commonly used in cosmetics, such as oils, waxes or othercommon fatty substances; standard gelling agents and/or thickeners;emulsifiers; moisturizers; emollients; sunscreens; hydrophilic orlipophilic active agents, for instance ceramides; free-radicalscavengers; surfactants; polymers; proteins; bactericides; sequesteringagents; antidandruff agents; antioxidants; preserving agents;fragrances; fillers; dyestuffs.

The amounts of these various adjuvants are those conventionally used inthe field under consideration.

Needless to say, a person skilled in the art will take care to selectthe optional compound(s) added to the composition according to theinvention such that the advantageous properties intrinsically associatedwith the composition in accordance with the invention are not, or arenot substantially, adversely affected by the envisaged addition.

The compositions according to the invention may be used in rinse-out orleave-in mode.

The compositions according to the invention may be in any form that issuitable for topical application, especially in the form of solutions ofthe lotion or serum type; in the form of aqueous gels; in the form ofemulsions obtained by dispersing a fatty phase in an aqueous phase (O/W)or, conversely, (W/O), of more or less thick liquid consistency such asmore or less unctuous milks and creams.

These compositions are prepared according to the usual methods.

The compositions according to the invention are preferably used as hairproducts, especially for holding the hairstyle or for shaping the hair.They may also give the hair a temporary coloration or provide the hairwith good protection against the effects of UV radiation, while at thesame time providing hair holding or fixing properties.

The hair compositions according to the invention are preferably stylingproducts such as hairsetting gels or lotions, blow-drying lotions, andfixing and styling compositions such as lacquers or sprays.

The lotions may be packaged in various forms, especially in vaporizers,in pump-dispenser bottles or in aerosol containers to allow anapplication of the composition in vaporized form or in the form of amousse. Such packaging forms are indicated, for example, when it isdesired to obtain a spray or mousse for fixing or treating the hair.

A subject of the present invention is also the use of the compositionaccording to the invention in a process for treating the hair, in orderto hold and/or color it.

According to one embodiment of this process, the composition is appliedto rinsed or unrinsed hair, preferably in the form of a spray, eitherusing a pump-dispenser bottle or using an aerosol.

After spraying onto the head of hair, the composition is left to act andto dry.

The hair may be rinsed after applying the composition.

The hair may be placed in the desired shape, either before theapplication or immediately after.

The drying time may be variable and depends on the nature of thecomposition.

After combing, the hair has a very pleasant feel quality.

The invention is illustrated by the examples that follow.

EXAMPLE 1

The four formulations below were prepared:

Water-soluble unpoly- Neutralizing agent merized or relativelyHydrochloric acid unpolymerized silicon (amount of neutral- compoundization (normality) Aminopropyltriethoxy- relative to the silane (g per100 g of amount of soluble Compositions composition) silane) Water 1 12g 0 qs 100 g 2 12 g 0.5 qs 100 g 3 12 g 0.25 qs 100 g 4 12 g 0.75 qs 100g

The silicon-29 NMR analysis shows that these two compositions containabout 10 g of organosilicon compounds containing one, two or threesilicon atoms per 100 g of composition (NMR peaks present at a chemicalshift ranging from −30 to −75 ppm (tetramethylsilane being used asreference)).

The four compositions are used in the following applications:

Application 1: Leave-in Application. Production of a Styling Effect.

The compositions are introduced into an aerosol can in a proportion of65 g. The aerosol can is fitted with a 51 P valve and a C0₂ 045diffuser. 35 g of dimethyl ether are added to each can.

Two locks of 5 g of natural hair are prepared. The hairs are held at theroots by a clip and are arranged in a triangle.

Compositions 1, 2 and 3 are sprayed onto the locks for 5 seconds perface. After drying (15 minutes), a panel of 8 trained testers evaluatesthe styling effect, on a scale from 0 to 50; 0 corresponds to no stylingeffect and 50 to a very strong styling effect.

A disentangling is performed and a panel of 8 trained testers evaluatesthe feel qualities of the locks thus treated.

The feel quality is graded on a scale from 0 to 50; 0 corresponds to avery poor feel quality and 50 to a very pleasant feel quality.

The grades from the 8 testers are totalled for each composition and theaverage is then determined.

The following results are obtained:

Average of the “feel Average of the “styling quality after dis-Compositions effect” grades entangling” grades 1 10 15 2 30 20 3 30 15

The results show that with the partially neutralized compositions, abetter styling effect and a feel quality after disentangling that is atleast equal to that of a non-neutralized composition are obtained.

Application 2: Leave-in Application. Production of a Styling Effect.

Two locks of 5 g of natural hair are prepared. The hairs are held at theroots and left free over the remainder of the length.

The compositions are placed in contact with the locks for 2 minutes (thelocks are immersed in 10 ml of the test solution). They are then left todry for 24 hours.

After drying, the hairs are stuck together in all cases.

A disentangling is performed and a panel of 8 trained testers evaluatesthe feel qualities of the locks thus treated.

The feel quality is graded on a scale from 0 to 50; 0 corresponds to avery poor feel quality and 50 to a very pleasant feel quality.

The grades from the 8 testers are totalled for each composition and theaverage is then determined.

The table summarizes the results:

Average of the “feel quality Compositions after disentangling” grades 110 2 25 3 25 4 15

The results show that with the partially neutralized compositionsaccording to the invention a better feel quality after disentangling isobtained, in leave-in application, compared with a non-neutralizedcomposition.

1. A cosmetic composition comprising, in a cosmetically acceptableaqueous medium, at least 0.02% by weight, relative to the total weightof the composition, of at least one substantially unpolymerizedwater-soluble organosilicon compound, the organosilicon compound being:a silane having one silicon atom having the formula:

in which: R₄ represents a halogen or an OR′ or R′₁ group: R₅ representsa halogen or an OR″ or R′₂ group; R₆ represents a halogen or an OR′″ orR′₃ group; R₁, R₂, R₃, R′, R″, R′″, R′₁, R′₂ and R′₃ represent,independently of each other, an acid substituted or unsubstituted,saturated or unsaturated, linear or branched hydrocarbon-based group,R₁, R₂, R′, R″ and R′″ may represent, independently of each other,hydrogen, at least two of the groups R₄ R₅ and R₆ being other than thegroups R′₁, R′₂ and R′₃, or a siloxane having two or three siliconatoms, the organosilicon compound having at least one basic chemicalfunction and at least two hydrolyzable or hydroxyl groups per molecule,the composition containing a sufficient amount of a neutralizing agentsuch that the organosilicon compound is neutralized to a proportion offrom 1/1000 to 99/100.
 2. The cosmetic composition of claim 1, whereinthe organosilicon compound represents at least 0.5% and up to 50% byweight of the composition.
 3. The composition of claim 1, wherein thebasic chemical function of the organosilicon compound is a primary,secondary or tertiary amine.
 4. The composition of claim 1, wherein thehydrolyzable groups are alkoxy, aryloxy or halogen groups.
 5. Thecomposition of claim 1, wherein the neutralizing agent is an acid. 6.The composition of claim 5, wherein the neutralizing agent ishydrochloric acid, nitric acid or a mono-, di- or tricarboxylic organicacid.
 7. The composition of claim 1, wherein the composition is in theform of a hair product.
 8. The composition of claim 7, wherein thecomposition is in the form of a hair product for holding the hair or forshaping the hair.
 9. The composition of claim 1, wherein theorganosilicon compound is neutralized to a proportion of from 0.2/100 to70/100.
 10. The cosmetic composition of claim 1, wherein theorganosilicon compound has the formula:

in which: R′₄ represents a halogen or an OR₁₁group; R₅ represents ahalogen or an OR″ or R′₂ group; R₆ represents a halogen or an OR′″ orR′₃ group; R₇ represents a halogen or an OR₁₀ or R″₁ group; R₉represents a halogen or an OR₈, R″₂ or R₃NR₁R₂ group; R₁, R₂, R₃, R″,R′″, R′₂ and R′₃ represent, independently of each other, a substitutedor unsubstituted, saturated or unsaturated, linear or branchedhydrocarbon-based group; R₁, R₂, R″ and R′″ may represent, independentlyof each other, hydrogen, at least two of the groups R₅ and R₆ beingother than the groups R′₂ and R′₃; R″₁, R″₂, R₈, R₁₀ and R₁₁ represent asubstituted or unsubstituted, saturated or unsaturated, linear orbranched hydrocarbon-based group; and R₁₁, R₁₀ and R₈ may represent,independently of each other, hydrogen, at least one of the groups R₆, R₇and R₉ denoting a halogen or an OR′″, OR₁₀ or OR₈ group.
 11. Thecosmetic composition of claim 10, wherein the groups R₁, R₂, R′, R′₁,R′₂, R′₃, R″, R′″, R″₁, R″₂, R₈, R₁₀ and R₁₁ are a C₁ to C₁₂ alkylradical, a C₆ to C₁₄ aryl radical, a (C₁ to C₈)alkyl(C₆ to C₁₄)arylradical or (C₆ to C₁₄)aryl(C₁ to C₈)alkyl radical.